Stabilization of hydrocarbon oils and novel additive therefor



United States Patent US. CI. 44-72 5 Claims ABSTRACT OF THE DISCLOSURE Hydrocarbon oil tending to deteriorate in storage and when heated containing an inhibiting amount of a reaction product of a epihalohydrin compound and an alkylamine in which the alkyl group is attached to the nitrogen atom at its beta carbon atom.

This invention relates to stabilization of hydrocarbon oils, and, more particularly, to the use of a novel additive to prevent degradation of hydrocarbon oils which normally is encountered when the hydrocarbon oil is exposed to oxygen and/ or heat.

While the present invention may be used for the stabilization of gasoline, naphtha or other relativelylow boiling hydrocarbon oils, it is particularly applicable to the stabilization of higher boiling hydrocarbon oils including fuel oil, diesel oil, jet fuel, etc. The fuel oils are marketed under various names including burner oil, furnace oil and, of course, various grades of fuel oil. During storage and/ or use, these oils undergo deterioration, with the formation of sediment, undesired discoloration, etc. The formation of sediment is objectionable because the sediment tends to plug strainers, burner tips, injectors, etc, and, when used as diesel fuel, tends to form varnish and sludge in the diesel engine. Discoloration of the oil is objectionable for various reasons, particularly the customers preference for light colored oils.

Deterioration of the jet fuel and burner oil at high temperature also is a serious problem. For example, jet fuel is used as a heat exchange medium for hot exhaust gases and deterioration of the jet fuel results in plugging of the exchanger coils. This problem of deposit formation in heat exchangers also occurs during the processing of hydrocarbon oils in which the hydrocarbon oil charge at a lower temperature is passed into indirect heat exchange with hot reaction products of the process. This serves the economic advantage of partially heating the charge to the process and of partially cooling the reaction products of the process. Here again, it is important that deposit formation be avoided or at least reduced to a minimum in order to permit satisfactory and continuous operation of the heat exchange system. Otherwise plugging of the tubes and/or shell of the heat exchanger will decrease heat transfer and eventually will require shutdown of the plant in order to clean the heat exchanger and, if necessary, to replace all or a portion of the heat exchange equipment.

In accordance with the present invention, the above difiiculties are avoided by incorporating the novel additive of the present invention into the hydrocarbon oil. The additive serves to retard and/or prevent degradation of the hydrocarbon oil in storage and/or in use, as well as during processing as hereinbefore described.

The novel additive of the present invention is the reaction product formed by the reaction of a particular type of amine with an epihalohydrin compound. The particular type of amine for use in forming the reaction product is critical and is a beta-alkyl amine, herein referred to as beta-amine, and is one in which the alkyl group is attached to the nitrogen atom at the beta or second carbon atom Patented July 22, 1969 of the alkyl group. It now has been found that the use of the beta-amine in preparing the reaction product of the present invention offers unexpected advantages over reaction products prepared when using alpha-alkyl amines, herein referred to as alpha-amines, in which the alkyl group is attached to the nitrogen atom at the terminal carbon atom of the alkyl group.

Very effective additives for hydrocarbon oils, particularly hydrocarbon oils higher boiling than gasoline, have been prepared by the reaction of alpha-amines with epihalohydrin compounds. While these additives are very effective, they do have the disadvantage of high pour point and high cloud point. In other words the reaction product tends to gel and solidify at ambient temperature, especially during the colder seasons of the year. When this occurs, it is objectionable because the user of the additive either must handle a product which is part liquid and part solid or the user must go through the added time and expense of heating the compound in order to form a liquid product. As can be well appreciated, this added requirement interferes with the ready use of the additive and, in some cases, may mean the difference between a decision to use the additive commercially or not to so use it.

As will be illustrated by the data in the examples appended to the present specifications, the reaction product prepared from the beta-amine is of considerably lower pour point and lower cloud point. Any suitable beta-amine is used as a reactant in preparing the novel additive of the present invention. In one embodiment the beta-amine is a monoamine and, while it may contain from 4 to about 50 carbon atoms, it preferably contains from about 6 to about 20 carbon atoms. Illustrative preferred beta-amines include l-methylpentylamine, l-methylhexylamine, l-methylheptylamine, l-methyloctylamine, l-methylnonylamine, l-methyldecylamine, l-methylundecylamine, l-methyldedecylamine, l-methyltridecylamine, l-methyltetradecylamine, l-methylpentadecylamine, l-methylhexadecylamine, l-methylheptadecylamine, l-methyloctadecylamine, l-methylnonadecylamine, etc.

It is understood that the long alkyl chain may be straight chain or may contain branching in the chain other than any additional carbon attachment to the beta carbon atom.

In another embodiment the beta-amine is a polyamine containing at least one beta-amine configuration. Illustrative preferred beta-diamines include N-l-methylpentyl-propylenediamine, N-1-methylhexyl-propylenediamine, N-l-methylheptyl-propylenediamine, N-l-methyloctyl-propylenediamine, N-l-methylnonyl-propylenediamine, N-1-methyldecyl-propylenediamine, N-l-methylundecyl-propylenediamine, N-l-methyldodecyl-propylenediamine, N-1-methyltridecyl-propylenediamine, N-l-methyltetradecyl-propylenediamine, N-1-methylpentadecyl-propylenediamine, N-1-methylhexadecyl-propylenediamine, N-1-methylheptadecyl-propylenediamine, N-1-rnethyloctadecyl-propylenediamine, N-1-methylnonadecyl-propylenediamine, etc.,

similarly substituted ethylcnediamines, butylenediamines, pentylenediamine, hexylenediamine, heptylenediamines, etc., as well as dialkylenetriamines, trialkylenetetramiries, tetraalkylenepentamines, etc., containing at least one beta-amine configuration. Here again, it is understood that the long alkyl chain may be straight chain or may contain branching along the chain other than additional carbon linkage on the beta carbon atom.

While the preferred beta-amines for use in accordance with the present invention are beta-alkyl amines, it is understood that the corresponding beta-alkylene amines may be used but not necessarily with equivalent results. The beta-alkylene amines, both monoamines and polyamines, will contain unsaturation in the long alkyl chain. Such beta-amines may result when they are prepared from unsaturated fatty acids.

The beta-amines are prepared in any suitable manner. In most methods of preparation a mixture of beta-amines may be formed and such mixture of beta-amines may be used for reaction with the epihalohydrin compound in accordance with the present invention.

As hereinbefore set forth the beta-amine is reacted with an epihalohydrin compound. Epichlorohydrin is preferred. Other epichlorohydrin compounds include 1,2-epoxy-4- chlorobutane, 2,3 epoxy 4 chlorobutane, 1,2-epoxy-5- chloropentane, 2,3-epoxy-5-chloropentane, etc. In general the chloro derivatives are preferred, although it is understood that the corresponding bromo and iodo compounds may be employed. In some cases epidihalohydrin compounds may be utilized. It is understood that the different epihalohydrin compounds are not necessarily equivalent and that, as hereinbefore set forth, epichlorohydrin is preferred.

The beta-amine is reacted with the epihalohydrin compound in a mole ratio of from 1 to 2 mole proportions of beta-amine to 1 to 1.5 mole proportions of epihalohydrin compound. In a particularly preferred embodiment of the invention, the beta-monoamine is reacted with epichlorohydrin in equal mole proportions, although an excess of one of the reactants may be used when desired. A preferred reaction product is a polymeric product prepared by reacting equal mole proportions of the amine and epichlorohyd-rin and contains from about 2 to 20 or more recurring units and preferably from about 2 to about recurring units.

The desired quantity of beta-amine epihalohydrin compounds may be supplied to the reaction zone and therein reacted, although generally it is preferred to supply one reactant to the reaction zone and then introduce the other reactant step-wise. Thus, usually it is preferred to supply the epichlorohydrin to the reaction zone and to add the beta-amine step-wise, with stirring. Preferably the reaction of epichlorohydrin with the second or later portions of beta-amine is effected at a higher temperature than with the first portion of the beta-amine. The reaction preferably is effected in the presence of a solvent which may comprise a hydrocarbon and particularly an aromatic hydrocarbon including benzene, toluene, xylene, ethylbenzene, cumene, etc., or an alcohol including ethanol, propanol, butanol, etc. In another embodiment the solvent may comprise a glycol including ethylene glycol, propylene glycol, glycerol, etc., or a saturated aliphatic hydrocarbon including hexane, heptane, octane, etc.

The reaction of the beta-amine and epihalohydrin is effected at any suitable temperature which generally will be within the range of from about 50 to about 200C. and preferably within the range of from about 60 to about 150 C. Conveniently, this reaction is effected by heating a solution of epichlorohydrin in aromatic solvent, with stirring, gradually adding the beta-amine thereto, and continuing the heating, preferably at a higher temperature until the reaction is completed, or the reverse order of adding the reactants may be used. In the preparation of the polymeric reaction product, the reaction mixture, following completion of the reaction of the beta-amine and epihalohydrin, is treated with an inorganic base in order to convert the organic halide salt of the reaction mixture to an inorganic halide salt and to thereby liberate the free amine for further reaction to form the desired polymeric product. This may be effected in any suitable manner and generally is accomplished by reacting the primary reaction product with a strong inorganic base such as sodium hydroxide, potassium hydroxide, etc., to form the corresponding metal halide. The reaction to form the metal halide is effected at a temperature within the range of from about 60 to about 200 C. and preferably from about to about 150 C. The inorganic base may be added in at least two steps with intervening heating and reacting so that organic halide formed after the first addition of inorganic base is in turn reacted to liberate the free amine.

In one embodiment the product at this stage of manufacture may be withdrawn from the reaction zone and filtered or otherwise treated to remove the inorganic halide. Generally, however, it is preferred to perform the next step in the same reaction zone Without removing the inorganic halide. At the conditions used in forming the polymeric reaction product, the inorganic halide is inert and, therefore, its presence is not objectionable. Regardless of whether or not the inorganic halide is removed, the primary reaction product of the amine compound and epihalohydrin compound is now further heated and reacted in order to form the desired linear polymeric reaction product. This further heating and reacting is .at a temperature of from about 75 to about 200 C. and preferably from about to about 150 C.

After formation of the desired polymeric reaction product or before this step as mentioned above, the inorganic halide salt is removed in any suitable manner, including filtering, centrifugal separation, etc. In some cases, it may be of advantage to effect the filtration at an elevated temperature which may range from about 35 to about C. or more. When desired, water or other aqueous solvent may be added to the reaction mixture to dissolve and facilitate removal of the inorganic halide salt.

The reaction product prepared in the above manner is a new composition of matter and accordingly, also is being so claimed in the present application. The reaction product is recovered as a viscous liquid which, as hereinbefore set forth, has a low pour point and low cloud point. Generally, it will range from a light through amber color, although, in some cases, it may be of a dark color. For most uses, the reaction product may be dissolved in a suitable solvent, particularly a hydrocarbon and, more particularly, an aromatic hydrocarbon. Accordingly, a convenient method is to allow the reaction product to be recovered in the solvent used during the manufacture thereof and, when necessary, to add additional solvent to form a final composition of the desired concentration of active ingredients. However, when desired, the solvent used during the reaction may be removed by vacuum distillation.

As hereinbefore set forth, the reaction product is particularly applicable for use as an additive to hydrocarbon oil. The additive will be used in hydrocarbon oil in a stabilizing concentration which will be below about 1% by weight and within the range of from about 0.0001% to about 1% and generally from about 0.001% to about 0.5% by weight. In another embodiment the reaction product of the present invention is used in admixture with certain metal deactivators which appear to increase the potency of the additive beyond that which normally would be expected and thus, results in a synergistic effect. A particularly preferred metal deactivator is disalicylaldiaminopropane. Other metal deactivators include o-hydroxybenzalaminophenol, o-hydroxybenzalanthranilic acid, alkylenepolyamine-tetracarboxylic acids and particularly ethylenediamine-tetracetic acid, or alkali metal salts thereof. The metal deactivator is used in a minor amount and, accordingly, in a concentration of below about 0.5% by weight and within the range of from about 0.00001% to about 0.5% and generally from about 0.0001% to about 0.05% by weight.

When desired the additive of the present invention also may be used in conjunction with other antioxidants, cetane improvers, rust inhibitors, etc. Generally, these additives are employed as solutions in suitable solvents and, when desired, the additive of the present invention may beprepared as a mixture with one or more other additives, preferably as a solution in a suitable solvent, and the same marketed and used as a single commodity of multiple purpose.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

Example I The reaction product of this example was prepared by the reaction of equal mole proportions of a beta-monoamine mixture and epichlorohydrin. The mixed betamonoamines used in this example are available commercially as Armeen L-7 and comprise a mixture of beta-monoamines containing from about 7 to about 11 carbon atoms per molecule. The mixture of beta-amines has an average molecular weight, of 145, an average number of carbon atoms per molecule of 9 and a basic nitrogen equivalent weight of 136 grams.

The reaction was efiected by first forming a solution of 93 g. (one mole) of epichlorohydrin in 70 g. of xylene solvent and heating the mixture to a pot temperature of 80 C. A separate solution of 136 g. of the mixed betamonoamines in 70 g. of xylene solvent was prepared. One-half of the latter solution (0.5 mole of amines) was added to the solution of epichlorohydrin with stirring and heating to a pot temperature of 8085 C. for about one hour, after which time the remaining solution of betamonoamine (0.5 mole) was added to the reaction mixture, followed by 60 grams of additional xylene solvent. The reaction mixture was stirred and heated to a pot temperature of about 110 C. for about 4 hours. At this time 80 g. of 50% sodium hydroxide solution (one mole) was added and the reaction mixture was heated and stirred at a pot temperature of about 110 C. for 3 /2 hours. Following completion of the reaction, 106 g. of water was added and the mixture was allowed to settle into two phases. Ready separation of phases occurred, the water phase containing the sodium chloride. The reaction product was shaken with 8 grams of adsorbent silica gel at 70-80 C. in order to clear up any haze and the mixture then was filtered and the reaction product was recovered as a light yellow clear liquid.

A portion of the reaction product prepared in the above manner was subjected to vacuum distillation to remove the xylene solvent, and the product was recovered as a light yellow clear liquid having an average molecular weight of 515 g., a basic nitrogen equivalent weight of 4.61, a tertiary basic nitrogen equivalent weight of 3.0 and an acidity of 0.242 meq./g. The reaction product had an average of 2.6 recurring units.

Example H The reaction product of this example was prepared in substantially the same manner as described in Example I except that the beta-monoamine used in this example was a mixture available commercially as Armeen L-9 and comprises a mixture of beta-monoamines containing from about 9 to about 13 carbon atoms per molecule. This mixture of amines has an average molecular weight of 167 g., an average number of carbon atoms per molecule of 11 and a basic nitrogen equivalent weight of 164 g.

The reaction was effected by first forming a solution of 93 g. (one mole) of epichlorohydrin in 93 g. of xylene solvent and forming a separate solution of 164 g. (one mole) of the amines in 82 g. of xylene solvent. As in the preparation of Example I, the epichlorohydrin solution was heated and the amine solution was added thereto in two separate portions. The reaction vessel was heated initially to a pot temperature of C. for about 1.5 hours and later to a pot temperature up to about 125 C. for about 8 hours. Following completion of the reaction, g. of water was added and the mixture was separated in the same manner as described in Example I, after which the reaction product was shaken with 4 grams of silica adsorbent and filtered. A portion of the reaction product was subjected to vacuum distillation to remove the xylene solvent, to leave the reaction product as a clear amber liquid having a total basic nitrogen equivalent weight of 4.24, a tertiary basic nitrogen equivalent weight of 3.61 and an acidity of 0.196 meq./g.

Example III The reaction product of this example was prepared in substantially the same manner as described in Example I, except that the beta-monoamine used in this example was a mixture available commercially as Armeen L-ll and comprises a mixture of beta-monoamines containing from about 11 to about 15 carbon atoms per molecule. This mixture of amines has an average molecular weight of 204 g., an average number of carbon atoms per molecule of 13 and a basic nitrogen equivalent weight of 204 g.

A solution of 74.5 g. (0.8 mole) of epichlorohydrin in 75 g. of xylene solvent was prepared. A separate solution of 162.8 g. (0.8 mole) of the amines in 81 g. of xylene solvent was separately prepared. The epichlorohydrin solution was heated to a pot temperature of 96 C., with stirring, and one-half of the amine solution was added thereto, with stirring and heating at about 100 C. for about one hour, after which the remaining portion of the amine solution was added with stirring and heating to a pot temperature of about 133 C. for about six hours. Then 64 g. of 50% sodium hydroxide solution was added with continuous stirring and heating to about 112 C. As in the previous preparations water, in this case 80 grams, was added to the reaction mixture, followed by settling and separation of layers and then shaking with 8 grams of silica adsorbent and filtering to produce a light yellowish clear product. A portion of the reaction product was subjected to vacuum distillation to remove the xylene solvent and to leave a clear yellowish liquid having an average molecular weight of 774 g., a basic nitrogen equivalent weight of 3.87, a tertiary basic nitrogen equivalent weight of 2.59 and an acidity of 0.096 meq./g. The reaction product had an average of 2.98 recurring units.

Example IV The reaction product of this example was prepared in substantially the same manner as described in the previous examples except that the beta-monoarnine used in this example was a mixture available commercially as Armeen L-15 and comprises a mixture of beta-monoamines containing from about 15 to about 22 carbon atoms per molecule. This mixture of amines has an average molecular weight of 270 g., an average number of carbon atoms per molecule of 20 and a basic nitrogen equivalent weight of 292 grams.

A solution of 56 g. (0.6 mole) of epichlorohydrin in 70 g. of xylene solvent was prepared. A separate solution of 174 g. of the beta-monoamine mixture in 87 g. of xylene solvent was prepared. The epichlorohydrin solution was heated to a pot temperature of C. with stirring and one-half of the amine solution was added and the mixture stirred and heated to a pot temperature of C. Thereafter the remaining portion of the amine solution was added and the mixture was stirred and heated to a maximum pot temperature of about C. for about 7 hours. Then 48 g. of 50% sodium hydroxide solution was added and the stirring and heating to a pot temperature starting at 145 and dropping to 116 C. over a period of about 3 /2 hours. Here again, water was added, the phases separated and the reaction product shaken with 8 grams of adsorbent silica gel and filtered. The reaction product was recovered as a clear light brown liquid.

A portion of the above reaction product was subjected to vacuum distillation to remove the xylene solvent and to leave the reaction product as an amber clear liquid having an average molecular weight of 659, a total basic nitrogen equivalent weight of 2.76, a tertiary basic nitrogen equivalent weight of 1.69 and an acidity of 0.076 10 meq./g. The reaction product had an average of 1.9 recurring units.

Example V The reaction product of this example is prepared by reacting equal mole proportions of N 1- methylheptylamine with epichlorohydrin. The epichlorohydrin is formed as a solution in toluene solvent and the N-l-methylheptylamine is formed as a separate solution in toluene solvent. The epichlorohydrin solution is stirred and heated to a temperature of 100 C. and one-half portion of the N-l-methylheptylamine solution is added thereto with stirring and heating to 100 C. Then the remaining N-lmethylheptylamine solution is added and the mixture is stirred and heated to 120 C. An equal mole proportion of by weight sodium hydroxide solution is added in increment portions with continued stirring and heating to a temperature of 125 C. Following completion of the reaction, the sodium chloride formed during the reaction is removed by filtering and the product is recovered as a solution in toluene solvent. Additional toluene solvent is added to form a final solution containing the active ingredient in a 50% by weight concentration.

Example VI The reaction product of this example is prepared by reacting one mole proportion of N-l-methyldecyl-pr0pyl ene-diamine with one mole proportion of epichlorohydrin. Here again, the epichlorohydrin and the amine are formed as separate solutions in xylene solvent. The epichloro hydrin solution is stirred and heated to a temperature of 80 C. and one-half of the amine solution is added thereto with stirring and continued heating at 80 C., after which the remaining portion of the amine solution is added with stirring and heating to a temperature of about 90 C. Following reaction of the epichlorohydrin and amine, an equal mole proportion of 35% by weight sodium hydroxide solution is added and the mixture is stirred and heated at 95 C. Following completion of the reaction, the reaction mixture is withdrawn and filtered hot to remove the sodium chloride formed during the reaction. The reaction product is recovered and subjected to vacuum distillation to remove the Xylene solvent and to recover the reaction product as a clear liquid.

Example VII Another reaction product is prepared in substantially the same manner as described in Example VI except that 50 the beta-diamine used is a mixture of beta-diamines marketed under the trade name of Duomeen L-ll. This mixture contains beta-diamines having from 14 to about 17 carbon atoms per molecule. The reaction is effected by forming separate solutions of epichlorohydrin in toluene 5 solvent and the beta-diamines in toluene solvent. The betadiamines are added in increment portions to the heated and stirred mixture of epichlorohydrin solution. Potassium hydroxide is added to form potassium chloride and to release the available amines for further reaction to form a polymeric reaction product. Following completion of the reaction, the reaction mixture is filtered to re move the potassium chloride and then is subjected to vacuum distillation to recover the reaction product as a clear liquid. 7 5

8 Example VIII As hereinbefore set forth, an unexpected and important advantage of the reaction products of the present invention prepared from the beta-amines is the low pour point, as well as the low cloud point. The pour point and cloud point of the reaction products of Examples I, II and III, prepared as solutions containing 50% by weight of active ingredients, are reported in the following table. For comparative purposes, the pour point and cloud point of the reaction product prepared from epichlorohydrin and alpha-amine (hydrogenated tallowamine) are also reported in the table. The reaction product prepared from the alpha-amine was made in substantially the same manner as described in Examples I through III except that the amine was an alpha-amine instead of a beta-amine.

TABLE I Pour point Cloud point Reaction product F.) C F.)

Example I 110 110 Example IL. 110 -110 Example III -110 110 Prepared from hydrogenated tallowamine +60 +62 Example IX As hereinbefore set forth, the additives of the present invention are particularly applicable for use in fuel oil. These were evaluated in various methods. In a one-day fuel stability test, 500 m1. of commercial No. 2 fuel oil are placed in a scaled bottle, into which 3 iron strips are also placed, and the system is purged with oxygen and sealed. The bottle then is heated at 212 F. for 16 hours, after which the fuel oil is allowed to cool, filtered and the deposit formation is determined by weighmg.

When evaluated in the above manner, a control or blank sample of the fuel oil, without additive, developed 15.4 mg. of deposit per cc. of fuel oil. The following table reports these data and the results obtained when other samples of the fuel oil containing the additive of the present invention were evaluated in the same manner. The additives of the present invention comprised 50% weight solutions in xylene solvent and were used in a concentration of 60 parts per million of the solution (30 parts per million of active ingredients).

As hereinbefore set forth, the additives of the present invention advantageously are used in admixture with a copper deactivator. The following table also reports results of evaluations made with samples of the fuel oil containing 60 parts per million of the additive solution (30 parts per million of active ingredients) and 2 parts per million of salicylal diaminopropane copper deactivator.

TABLE II Deposit formation mg. of deposit Additive: per 100 cc. of oil None 15.4 60 p.p.m. of Example I solution 2.5 60 p.p.m. of Example II solution 4.2 60 p.p.m. of Example III solution 3.4 60 p.p.m. of Example I solution plus 2 p.p.m.

salicylal diamino-propane 0.2 60 p.p.m. of Example II solution plus 2 p.p.m.

salicylal diamino-propane 0.3 60 p.p.m. of Example III solution plus 2 p.p.m.

salicylal diamino-propane 0.4

From the data in the above table it will be seen that the control sample, without additive, developed 15.4 mg. of deposit per 100 cc. of fuel oil. In contrast, the samples contatining 60 parts per million of the additive solutions of the present invention reduced these deposits to less than about 4 mg. per 100 cc. of fuel oil.

The table also shows the synergistic effect obtained by using the additive solution in admixture with the copper deactivator. This combination reduced the deposit formation'to less than about 0.4 mg. of deposit per 100 cc. of oil.

For comparative purposes, a sample of the fuel oil containing 60 parts per million of a 50% by weight reaction product solution prepared in substantially the same manner but using alpha-amine (hydrogenated tallowamine), when evaluated in the same manner, developed 4.8 mg. of deposit per 100 cc. of oil. Another sample containing 60 parts per million of this reaction product and 2 parts per million of salicylal diaminopropane developed 2.0 mg. of deposit per 100 cc. of oil. It will be noted that in this case the combination of reaction product and copper deactivator did not exhibit the high synergistic action which was experienced in the case of the mixture of copper deactivator and reaction products prepared from beta-amines.

Example X The additives of the present invention also were evaluated in a three-month fuel oil stability test in which samples of the fuel oil, with and without additives, were stored in Pyrex Erlenmeyer flasks in the dark for three months at 110 F., after which time the fuel oil was allowed to cool, then filtered and the deposit weighed. The fuel oil used in this series of tests was a commercial No. 2 fuel oil having a specific gravity of 0.8628 and a boiling range of from 399 to 628 F. The results of these evaluations are reported in the following table.

TABLE III Deposit formation mg. of

Additive: deposit per 100 cc. of oil None 3.2 32 p.p.m. of additive solution of Example I 0.5 32 p.p.m. of additive solution of Example II 0.2 32 p.p.m. of additive solution of Example III 0.4 32 p.p.m. of additive solution of Example IV 0.5

Here again, it will be noted that the additive solutions of the present invention were very effective in retarding deposit formation of the fuel oil during storage.

Example XI A 50% by weight solution in xylene solvent of the reaction product, prepared as described in Example I, is used as an additive to prevent heat exhcanger deposits in a gasoline reforming unit in which the gasoline is heated to a temperature of 890 F. and passed, together with hydrogen, through a reaction chamber containing a bed of catalyst comprising alumina-platinum-combined halogen. A series of three heaters and reaction chambers are used. The reaction products from the last reaction chamber are passed in indirect heat exchange with the gasoline charge to the process. This serves to partially cool the hot reaction products and to partially heat the incoming gasoline charge. Difiiculty is experienced because of deposit formation in the heat exchanger tubes. In order to minimize such deposit formation and to considerably extend the operability of the heat exchanger, 8 parts per million of the additive solution of Example I are incorporated in the hot reaction products leaving the reaction chamber prior to entering the heat exchanger.

I claim as my invention:

1. Hydrocarbon oil tending to deteriorate in storage and when heated containing, as an inhibitor against such deterioration, a stabilizing concentration of the reaction product of an epihalohydrin compound and an alkyl amine in which the alkyl group is attached to the nitrogen atom at its beta carbon atom.

2. The composition of claim 1 wherein said reaction product is formed at a temperature of from about 50 to about 200 C. by the reaction of from about 1 to 2 mole proportions of said alkyl amine with from 1 to about 1.5 mole proportions of epihalohydrin compound.

3. Hydrocarbon oil tending to deteriorate in storage and when heated containing, as an inhibitor against said deterioration, a stabilizing concentration of the reaction product formed at a temperature of from about 50 to about 200 C., from 1 to 2 mole proportions of a beta-amine containing from about 4 to about 50 carbon atoms with 1 to 1.5 mole proportions of epichlorohydrin, said amine having an alkyl group attached to the nitrogen atom at its beta carbon atom.

4. The composition of claim 3 further characterized in that said reaction product is treated with a strong inorganic base and further heated at a temperature within the range of from about to about 200 C.

5. The composition of claim 3 further characterized in that said reaction product is formed at a temperature of from about 60 to about C.

References Cited UNITED STATES PATENTS 2,361,339 10/1944 White et al. 44-73 3,189,652 6/1965 Pollitzer 44-72 DANIEL E. WYMAN, Primary Examiner Y. H. SMITH, Assistant Examiner US. Cl. X.R. 

